Process for the protection of textiles



United States Patent Ofiice 3,:l 453M Patented Dec. 31, 1953 Myinvention relates to a method of protecting textiles against the actionof noxious organisms such as fungi and bacteria which protection isretained after repeated washing and cleaning operations. Moreparticularly my invention relates to a method of protecting textiles byimpregnating or coating the textiles with mixtures selected from thegroup consisting of neomycin and bacitracin, zinc neomycin andbacitracin, zinc bacitracin and neomycin, zinc bacitracin and zincneomycin, copper neomycin and copper bacitracin, copper neomycin andbacitracin, and neomycin and copper bacitracin.

The textile industry has long sought a satisfactory means for protectingtextiles against the action of noxious organisms such as fungi andbacteria during periods of storage and use and after repeated washingand cleaning operations which eventually remove the protecting agentspreviously available. The problem has been complicated by the variouscompositions of textiles in use and the widely different conditionsunder which they require protection. For example, the practical utilityof textiles protected from bacterial activity, even after repeatedwashings, is obvious. The antibacterial properties of such textiles tendto lessen the liability of body odors due to the bactewhich contaminateuntreated fabrics and which thrive upon perspiration and other bodysecretions. Also, there would be prevention of or lessening of theconversion of urea to ammonia in urine-contamincd personal wear andespecially of diapers worn by infants or under clothing of older people.Clothing made from such textiles would help prevent infections due topathogenic fungi growing on the skin of the feet, crotch, or otherareas. Many compounds have been found to give initial protection totextiles, but they have not been universally employed due to the factthat they require either complicated fixation processes or they areeasily washed from the textiles by detergents and solvents used incleaning. Also, while some compositions could be applied easily andwould give lasting protection after repeated cleaning operations, they rere only effective against specific fungi and bacteria thus limitingtheir usefulness.

l have now discovered a new type of textile protective agent which isrelatively free from the defects of previously available textileprotectants and which can be easily and inexpensively applied totextiles and not readily removed therefrom by detergent and solventaction during normal cleaning.

.l have now discovered that mixtures selected from the group consistingof neomycin and bacitracin, zinc neomycin and bacitracin, zincbacitracin and neomycin, zinc bacitracin and zinc neomycin, copperneomycin and copper bacitracin, copper neomycin and bacitracin, andneomycin and copper bacitracin, effectively protect textiles againstnoxious organisms such as fungi and bacteria, the two antibiotics ineach mixture acting cooperatively in such a Way that the totaleffectiveness of the mixture is greater than the sum of the effects ofeach antibiotic when used independently.

Neomycin, which is actually a mixture of two very closely relatedantibiotics known specifically as neomycin B and neomycin C, is producedby a soil organism of the streptomyces group similar to Streptomycesfradiae when grown in nutrient media.

Bacitracin is produced by the organism, Bacillus subtilis, whenpropagated in various liquid nutrient media.

The zinc and copper salts of bacitracin and neomycin are prepared bytreating an aqueous solution containing either bacitracin or neomycinwith zinc chloride or copper chloride and a base such as sodiumhydroxide to precipitate either the zinc bacitracin, zinc neomycin,copper bacitracin or copper neomycin.

Although the compounds utilized in my process can be applied in anydesired order, it is preferable, when applying free neomycin or freebacitracin in combination with a zinc or copper salt of either neomycinor bacitracin, to

rst apply the zinc or copper salt to the textile. The textile can besuitably treated with a zinc or copper salt of either neomycin orbacitracin by placing the textile in an aqueous solution of bacitracinor neomycin, adding a solution of about 1.0% zinc chloride or copperchloride, adjusting the pH of the combined solutions with sodiumhydroxide to precipitate the zinc salt onto the textile, removing thetextile from the solution and allowing the thus treated textile to dry.After drying the textile it can be treated with either free neomycin orfree bacitracin by placing the textile in a solution of neomycin orbacitracin preferably using as the solvent a lower alcohol such asmethanol or butanol, removing the textile from the solution, andallowing the thus treated textile to dry.

When mixtures of free neomycin and free bacitracin are utilized, theycan be applied by placing the textile in a solution of neomycin andbacitracin preferably using as the solvent lower alcohols such asmethanol or butanol, etc., removing the textile from the solution, andallowing the thus treated textile to dry.

When mixtures of zinc bacitracin and zinc neomycin or copper bacitracinand copper neomycin are desired, the textile can be suitably treated byplacing it in an aqueous solution of bacitracin and neomycin, adding asolution of about 1.0% zinc chloride or copper chloride, adjusting thepH of the combined solutions with sodium hydroxide to precipitate eitherthe zinc or copper salts onto the textile, removing the textile from thesolution and allowing the thus treated textile to dry.

The exact quantity of the above mixtures to be utilized in treatingtextiles will vary widely and to a certain extent will depend upon thetype of textile in which the material is to be employed and theparticular noxious organism from which protection is desired. ingeneral, however, i have found that concentrations of the abovementionedmixtures as low as 0.05% by weight based on the weight of the textiletreated are sufiicient to protect textiles. For some requirements,however, concentrations ranging up to and above 1.0 to 2.0% aredesirable. How ever, I prefer to use concentrations ranging from about0.1 to about 1.0%.

The ratios of neomycin or its copper or zinc salts to bacitracin or itscopper or zinc salts in the above-mentioned concentrations also can varyWidely and will depend upon the particular noxious organism from whichmaximum protection is desired. Generally, however, I have founddesirable results are obtained when the textiles are impregnated withthe above concentrations of the mixtures in the relative proportions offrom about units of neomycin containing compound: 1 unit of bacitracincompound to 1 unit of neomycin containing compound: 5 units ofbacitracin containing compound.

I have found the above-mentioned mixtures to be safe for use in contactwith the skin and even with open wounds. Hence, textiles coated withthese compounds are particularly useful Where great personal hygiene isrequired. They are particularly efficacious in th treatment of and inthe prevention of infections, therefore making them especially adaptedfor use in hospitals and for bandages.

The following examples further illustrate my invention by showing theaction of my mixtures in protecting textiles against the organisms M.flax as and B. subtllis. However, i do not int nd to be limited to theprocesses, amounts, or procedures disclosed therein.

Example I To test the resistance of fabrics treated with combinations ofneomycin and Zinc bacitracin, three strips of cotton-duck fabric wereplaced in an aqueous solution of bacitracin; a 1.0% solution of zincchloride was then added and the pH was adjusted with sodium hydroxide toprecipitate zinc bacitracin onto the fabric. "iftCf su'l'ficientsoaking, the strips were drained and allowed to dry. The treated stripscontained 0.5% zinc bacitracin by weight based on the weight of thestrip. The strips were then placed in a methanolic solution of neomycin.After sufficient soaking, the strips were drained and allowed to dry.The treated strips contained about 0.2% neomycin by weight based on theweight of the strips. All three of the thus treated strips were washedand dried a total of thirteen times in an automatic washer using acommon household det rgent. At the end of the thirteenth washing anddrying procedure, one disc 25 mm. in diameter was cut from each of thestrips and each was placed on a separate dish 100 mm. in diameter eachcontaining ml. of nutrient agar inoculated with 0.1 ml. of the organismM. flavus and 0.1 ml. of the organism B. subtilis. The discs were thenincubated at 37 C. for 92 hours. At the end of the incubation period, itwas observed that no organisms were growing on any of the treated discs.

Example 11 To demonstrate the abilty of combinations of neomycin andcopper bacitracin in protecting textiles from noxious organisms, theprocedure of Example I was followed except that copper chloride wasutilized instead of zinc chloride. Inhibitory results similar to thoseshown in Example I were observed.

Example 111 To test the resistance of fabrics treated with combinationsof zinc neomycin and bacitracin, three strips of cotton-duck fabric wereplaced in an aqueous solution of neomycin; a 1.0% solution of zincchloride was then added and the pH was adjusted with sodium hydroxide toprecipitate zinc neomycin onto the fabric. After sufiicient soaking, thestrips were drained and allowed to dry. The treated strips contained0.4% zinc neomycin by weight based on the weight of the strip. Thestrips were then placed in a methanolic solution of bacitracin. Aftersufficient soaking, the strips were drained and allowed to dry. Thetreated strips contained about 0.3% bacitracin by weight based on theweight of the strips. All three of the thus treated strips were washedand dried a total of thirteen times in an automatic washing machineusing a common household detergent. At the end of the thirteentthwashing and drying procedure, one disc 25 mm. in diameter was cut fromeach of the strips and each was placed on a separate dish 100 mm. indiameter each containing 15 ml. of nutrient agar inoculated with 0.1 ml.of the organism M. flavas and 0.1 ml. of the organism B. subtilis. Thediscs were then incubated at 37 C. for a period of 72 hours. At the endof the 72-hour period, no growth was observed on any of the discs.

Example IV To demonstrate the ability of combinations of copper neomycinand bacitracin in protecting textiles from noxious organisms, theprocedure of Example III was followed except that copper chloride wasutilized instead of Zinc chloride. Inhibitory results similar to thoseshown in Example I were observed.

Example V To test the resistance of fabrics treated with combinations ofneomycin and bacitracin, three strips of cotton-- duck fabric wereplaced in a methanolic solution containing bacitracin and ncomycin.After sufficient soaking, the strips were drained and allowed to dry.all tnree of the thus treated strips were washed and dried a total ofthirteen times in an automatic washer using a common householddetergent. At the end of the thirteenth washing and drying procedure,one disc 25 mm. in diameter was cut from each of the strips and each wasplaced on a separate dish mm. in diameter each containing 15 ml. ofnutrient agar inoculated with 0.1 ml. of the organism M. flavas and 0.1ml. of the organism B. salatz'lls. The discs were then incubated at 37C. for 72 hours. At the end of the 72-hour period, no growth wasobserved on any of the discs.

Example V1 To test the resistance of fabrics treated with combinationsof zinc bacitracin and zinc neomycin, three strips of cotton-duck fabricwere placed in an aqueous solution of bacitracin and neomycin; a 1.0%solution of zinc chloride was then added, and the pH was adjusted withsodium hydroxide to precipitate zinc bacitracin and Zinc neomycin ontothe fabric. fter sufilcient soaking, the strips were drained and allowedto dry. All three of the thus treated strips were washed and dried atotal of thirteen times in an automatic washer using a common householddetergent. At the end of the thirteenth washing and drying procedure,one disc 25 mm. in diameter was cut from each of the strips and each wasplaced on a separate dish 100 mm. in diameter each containing 15 ml. ofnutrient agar and inoculated with 0.1 ml. of the organism M. flavus and0.1 ml. of the organism B. sabtilis. The discs were then incubated at 37C. for a 72-hour period. At the end of the incubation period, it wasobserved that no organisms were growing on any of the treated discs.

Example V11 To demonstrate the ability of combinations of copperneomycin and copper bacitracin in protecting textiles from noxiousorganisms, the procedure of Example VI was followed except that copperchloride was utilized instead of Zinc chloride. Inhibitory resultssimilar to those shown in Example Vl were observed.

Now having described my invention, what I claim is:

1. A process for protecting textiles against noxious organisms, saidprotection being retained after repeated cleaning operations whichcomprises treating the textiles with mixtures selected from the groupconsisting of neomycin and baotracin, zinc neomycin and bacitracin, zincbacitracin and neomycin, zinc bacitracin and zinc neomycin, copperneomycin and copper bacitracin, copper neomycin and bacitracin, andneomycin and copper bacitracin.

2. The process of claim 1 wherein the textiles are treated with saidneomycin and bacitracin by contacting said textiles in an alcoholicsolution, and with said neomycin and macitracin-containing compounds bycontacting said textiles in an aqueous solution.

3. A process for protecting textiles against noxious organisms, saidprotection being retained after repeated cleaning operations whichcomprises treating the textiles with from about 0.05 to about 2.0% byweight based on the weight of the textile of a mixture selected from thegroup consisting of neomycin and bacitracin, zinc neomycin andbacitracin, zinc bacitracin and neomycin, zinc bacitracin and zincneomycin, copper neornycin and copper bacitracin, copper neomycin andbacitracin, and neonrycin and copper bacitracin.

4-. The process of claim 3 wherein the ratio of neornycin containingcompounds to bacitracin containing compounds ranges from about 100 unitsof ncomycin containing compound: 1 unit of bacitracin containingcompound to 1 uint of neomycin containing compound: 5 units ofbacitracin compound.

5. The process of claim 3 wherein the textiles are treated with fromabout 0.1 to about 1.0% by weight based on the weight of the textile ofa mixture selected from the group consisting of neomycin and bacitracin,Zinc neomycin and bacitracin, zinc bacitracin and neomycin, zincbacitracin and zinc neomycin, copper neomycin and copper bacitracin,copper neomycin and bacitracin, and neomycin and copper bacit'racin.

6. The process of claim 3 wherein the mixture is neomycin andbacitracin.

7. The process of claim 3 wherein the mixture is zinc neomycin andbacitracin.

8. The process of claim 3 wherein the mixture is zinc bacitr acin andneomycin.

9. The process of claim 3 wherein the mixture is copper neomycin andcopper bacitraoin.

10. The process of claim 3 wherein the mixture is copper neomycin andbacitracin.

11. The process of claim 3 wherein the mixture is neomycin and copperbacitracin.

12. The process of claim 3 wherein the mixture is zinc neomycin and zincbacitracin.

13. The process of claim 3 wherein the textiles are treated with saidneomycin and bacitracin by contacting said textiles in an alcoholicsolution, and with said neomycin and bacitracin-containing compounds bycontacting said textiles in an aqueous solution.

14. A textile fabric being provided with protection against the actionof noxious organisms said protection being retained after repeatedcleaning operations comprising textile fibers impregnated with a mixtureselected from the group consisting of neomycin and bacitracin, zincneomycin and bacitracin, zinc bacitracin and neomycin, Zinc bacitracinand zinc neomycin, copper neomycin and copper bacitracin, copperneomycin and bacitracin and neomycin and copper bacitracin in amountssufiicient to provide such protection.

15. The textile fabric of claim 14 wherein the fibers are cotton fibers.

16. The textile fabric of claim 14 wherein the fibers are impregnatedwith said mixture in amounts such that the fabric contains about 0.05 to2.0 percent by weight of said mixture.

17. The textile fabric of claim 14 wherein the ratio ofneomycin-containing compounds to bacitracin-containing compounds rangesfrom about units of neomycin containing compound: 1 unit ofbacitracin-containing compound to 1 unit of neomycin-containingcompound: 5 units of bacitracin compound.

18. A process for protecting textiles against noxious organ-isms, saidprotection being retained after repeated cleaning operations whichcomprises treating with mixtures of free bacitracin, free neomycin,neomycinand bacitracin-containing compounds selected from the groupconsisting of neomycin and bacitracin, zinc bacitracin and neomycin,zinc bacitracin and zinc neomycin, copper neomycin and copperbacitracin, copper neomycin and bacitracin, neomycin and copperbacitracin, said free neomycin and free bacitracin contacting saidtextiles in an alcoholic solution subsequent to said neomycin andbaoitracin-containing compounds contacting said textiles in an aqueoussolution.

References Cited in the file of this patent UNITED STATES PATENTS2,633,446 King Mar. 31, 1953 2,680,701 Cosumano June 8, 1954 2,803,584Hodge Aug. 20, 1957 2,809,149 Consumano Oct. 8, 1957 2,813,056 DavisNov. 12, 1957 2,813,059 Davis Nov. 12, 1957 2,830,011 Parker et al. Apr.8, 1958 2,951,766 White Sept. 6, 1960

1. A PROCESS FOR PROTECTING TEXTILES AGAINST NOXIOUS ORGANISMS, SAIDPROTECTION BEING RETAINED AFTER REPEATED CLEANING OPERATIONS WHICHCOMPRISES TREATING THE TEXTILES WITH MIXTURES SELECTED FROM THE GROUPCONSISTING OF NEOMYCIN AND BACITRACIN, ZINC NEOMYCIN AND BACITRACIN,ZINC BACITRACIN AND NEOMYCIN, ZINC BACITRACIN AND ZINC NEOMYCIN, COPPERNEOMYCIN AND COPPER BACITRACIN, COPPER NEOMYCIN AND BACITRACIN, ANDNEOMYCIN AND COPPER BACITRACIN.